Resinous composition and method of forming the same



i) HLFLDLHUL UH slun- Patented 19 34 1 UNITED STATES PATEN'll orrlcsRESINOUS COMPOSITION AND METHOD OF FORLIING THE SAME Arthur 8. Ford, NewYork, N. Y., assignor to Industrial Sugar Products Corporation, NewYork, N. Y., a corporation of Delaware No Drawing. Application June 10,1931, Serial No. 543,486

14 Claims. (Cl. 260-3) This invention relates to a process for the for-Av further feature of the invention resides in mation of a novelcomposition of matter, and the production of a novel composition ofmatter the composition of matter thereby formed. which is transparentand water-white, which According to the invention, the process issuswill adhere with great tenacity to glass when I ceptible of numerousvariations in the quantities brought in contact therewith in liquid formand and character of the ingredients involved, and pe m tt d to hardenWhile n Such a a d these variations of the process produce, accordingwhich has an index of refraction substantially to the invention,products of differing characterthe sam as tha 0! a A n y V r u isticswhich have various uses in the arts. articles of commerce composed inpart of glass It is one of the feat es of this invention that and inpart of my novel compositon of matter 66 a hard, strong and d bleresinous or plastic may be produced, in accordance with theinvensubstance is produced which takes a number oi. tion, wherein theglass and my composition of forms and has diflering physical propertiesand matter are combined in a unitary structure havfields of usefulness.In one of the various forms in t app a an and fun t n f a n l piec 16which this invention may take, there is produced 0 as 70 a hard,water-white, transparent substance Other features, objects andadvantages of the which resembles glass in its appearance, whichinvention will appear n connection with the may be molded under pressureto form objects of descripti n Wh is iv wany shape, which can be pouredinto molds when This application s a c ml in p Of .20 freshly preparedand allowed to harden therein, my co-pending application Serial Number 7l which when hardened will not soften again at 38 ,230, fi ed Aug st 7,929, for Sy t the temperatures of formation, which is slightly i sn anapp i c 'fi b me On e date elastic, will not shrink, crack or discoloron proherewith and identifiedas S. N. 543,484, I dislonged exposure tothe air or to sunlight, and close and claim a resinous or adhesivesubstance which will transmit ultra violet light to an exmade by thecondensation or reaction together tent approximating that of quartzcrystal. of a saccharide and an aldehyde in aqueous solu-* Anotherfeature of the invention lies in the ti n. In n applic i n fi y me n v nd production of a glass-like substance which is herewith and identifiedas S. N. 543,485, I dis-.

1 transparent and water-white in substantial close and claim'awater-insoluble resinous sub- 30. thicknesses exceeding two or threeinches, yet stance made by the condensation or reaction towhich has hightensile strength and great elasg th r of an nhy r sacoharide nd ananticity, and which is adapted to be used in the hydrous aldehyde suchas paraformaldehyde. I packaging of goods and merchandise where it is Itis a feature of the present invention that desired to combine strengthand protection in a saccharide is first condensed or reacted with 35 thepackage with complete visibility of .the conan aldehyde, and theresultant condensation 9 tents. product, either with or without theaddition of A further feature of the invention is the proa methylene.hardening agent, is condensed or duction of a plastic or resinoussubstance havreacted with urea. The final condensation prodingglass-like characteristics of strength and uct so obtained, according tomy invention, is

40 transparency combined with a greater degree of a clear water-whitefluid which will harden into flexibility than glass, which can-be madecheaply I a glass-like transparent substance which is the andeconomically from raw materialsof relatively novel composition of matterof this invention. small cost and commercially available in large Afurther feature of my invention resides in quantities. the method bywhich the second stage of the 46 A further feature of the invention isthe proreaction of my invention is carried out in order duction of aplastic molding powder capable of to avoid explosive destruction of theapparatus being combined with various inert fillers or other or theformation of opaque products and to preplastics or resins or. gums toform when hot serve the water-white transparent characterispressed,various articles of utility in various novel tics of the resin which isproduced.

50 eilects and shades derived from the fact that A further feature of myinvention resides in the molding powder itself is water-white. and theproduction of a molding powder formed by transparent and when hotpressed forms a hard the pulverization of the hardened product of theglass-like body inwhich other objects or subsecond stage ofcondensation, above referred to,

stances may be permanently and visibly suswhich may be incorporated withinert fillers,

55 pended. such as powdered glass wool, which are them no mation ofmolded objects from mixtures of said molding powderwith'such fillers toform articles having the appearance of pearl or ivory or opal or areclear and transparent.

In accordance; with the present, invention a saccharide, or 'a substancecontainingja saccharide including particularly but not by way oflimitation, cane sugar, invert sugar, glucose, saccharose, levulose,molasses (for the production of a dark brown or black resin oradhesive), or chopped sugar cane which has 'not been freed of sap (forthe production preferably of opaque filled resinous masses) or othermono or disaccharides, is caused to react with a reagent such as analdehydic substance or a substance.

capable of producing an aldehyde, such as formalin, paraformaldehydeor'oxymethylene, furfural, or formaldehyde gas, or with an aromaticamine, such as anilin oil. Any one of the saccharides mentioned may beused singly, or two or more of the same may be mixed. Any one of thereagents named above for reaction with the saccharides may be usedsingly, or two or more thereof may be mixed. The reaction takes place inthe presence of a suitable solvent, the use of water being preferred inthe practice of the invention.

In the examples which are set forth below I have indicated exactquantities of materials which may be used in the successful carrying outof this invention, but these are illustrative only as the quantitiesinvolved may be varied within considerable limits to produce substanceshaving different physical characteristics. I have found that a largeamount of the aldehyde or equivalent substance in excess of thequantities stated in the examples is not harmful, as the excess appearsto be driven ofi upon heating. On the other hand, an excess of thesaccharide produces a resin which remains sticky and tacky on its outersurface and will not harden properly.

I do not know the nature of the reaction which takes place between thesaccharide and the aldehyde, but it'would appear that the sugar is fullyconsumed as the-reaction mass which is produced does not have theordinary physical characteristics of sugar, nor does it have most of thechemical characteristics thereof though it will rotate the plane oftransmitted light.

The sugar and the aldehyde, or the equivalents of either, may be mixedtogether in solution and gradually heated, taking care that the sugardoes not caramelize. In one form of the invention I may react togethercane sugar and a 36% solution of formaldehyde gas in water. As thetemperature is raised there is a slow .evolution of formaldehyde gas.Finally a'point is reached at which there is a sudden and large increaseof ebullition with substantial evolution of gas. This continues for ashort time and then, though the temperature is maintained constant ormaterially increased, the liquid becomes quiet and there is no furthersubstantial evolution of gas. It would appear that when this stage isreached some reaction has taken place between the sugar and theformaldehyde because thereafter the temperature of the liquid may beraised to substantially higher ranges without caramelizing effect. Sugarcaramelizes above 100 C. ordinarily, but after the reaction indicatedabove the temperature of the liquid may be raised above 300 withoutcaramelizing effect.

inasmuch as the-reaction between the sugar and the aldehyde preferablyoccurs without caramelization of the sugar, the reaction will take placebelow 100 0. when dry sugar and a dry aldehyde are used, and will takeplace below caramelization temperature when water is present as in caseof the use of formaldehyde gas dissolved --in water. Accordingly, areferenceherein to a substance .capable of "producing, an aldehyde isintended as a reference to a substance which will yield an aldehyde atthe reaction temperature,

e. g., at temperatures in the neighborhood of 100 C. to 150 C.

Upon completion of the preliminary condensation or reaction between thesaccharide and the aldehyde as set forth above, there is then added totheresultant condensation or reaction mass during constant heating asuitable quantity of urea, added in very small quantities at intervalswith constant stirring or agitation of the liquid in order to insure thecomplete solution and absorption of each installment of urea before theaddition of a subsequent installment thereof. It seems tqbe desirable,according to my observation, that the condensation reaction be carriedout in a vessel of aluminum o'nin the presence of aluminum or such othermetalas will maintain the hydrogen ion concentration at a suitable valueto prevent the formation of insoluble white precipitates.

The quantities of urea which should be added aresusceptiblc of variationwithin considerable limits, and variations in the quantity thereofaffect the hardness of the end product. There is, however, a definiteupper limit of quantity which can be introduced arising from the factthat an excess of urea, above this limit, will cause the formation of awhite precipitate which cannot be reabsorbed or dissolved by furtherheating and which makes the end product white and opaque. This upperlimit of quantity must, therefore, be approached as nearly as may be,but'not exceeded, if it is desired to produce a waterwhite glass-likesubstance of substantial hardness. 'On the other hand, by diminishingthe quantityof urea, or in other words retreating from the upper limitof quantity which will preserve'water-white transparency, an end productmay be obtained which is softer and more resilient in texture. Theamount of urea must therefore be left to experiment and individualadjustment, within the scope of my invention, in each case. It issuflicient to state here that an amount opaque and densely white. Noamount of further heating will serve to dissolve or clear up the whiteprecipitate into which the mass has thus been converted. It is,accordingly, a feature of the present invention so to introduce the ureainto the water-white liquid resultingfrom the condensation of thesaccharide and the aldehyde as to maintain the clear and water-whitecharacteristic thereof and to avoid the formation of the opaque whitemass or precipitate.

This is accomplished by the careful introduction of the urea in a number(say, a dozen) of portions or installments with constant stirring andheating, and permitting a lapse oftwo or that it be sprinkled lightly onthe surface during constant agitation of the body of the entire reactionmass. If, on the addition of any installment, a white cloudinessappears, I have found that no additional amount of heating will effectthe dissolution thereof, but the reaction mass can be saved by immediatefiltration thereof to eliminate the white precipitate. After filtrationthe further portions of the urea may be added and got into solutionunless the upper limit of quantity already referred to has been reached.

Upon the addition of each successive portion of urea a strong evolutionof gas takes place which decreases as soon as the portion of the.ureaadded has reacted or combined with the contents of the vessel. Duringthe addition of the urea the reaction mass becomes noticeably thicker,though retaining its water-white characteristic. Upon the addition ofthe final portion of urea the mass is ready for pouring. When the ureahas been got into solution in the reaction mass, thickening progressesvery rapidly while the elevated temperature is maintained until the masswill not pour.

If the reaction mass is transferred into molds while still in conditionto be poured, the retained heat will cause rapid hardening. If quicklyand mechanically cooled while still in condition to be poured it may bekept in this condition indefinitely out of contact with the air. Onsubsequent bons so as to form a large contact with air it solidifies toan extent suflicient to permit pulverization into fine particles whichconstitute a useful molding powder.

The molding powder thus formed may be pressed into molds under apressure of 1000 to 2000 pounds and at temperatures of from 150- 350 C.according to the moisture content of the powder. Under these conditionsthe particles will flow together in the mold and form a hard glasslikesubstance, transparent and waterwhite in substantial thicknesses, havinghigh tensile strength, and being tough and highly elastic like glass. upto 500-550 C..but will char slightly when subjected to a flame in theopen air. It is insoluble in acetone, amyl acetate, alcohol, ether ortoluol, but the surface is softened slightly after prolonged immersionin water. Formed in a thick pane like glass, .it is completelycolorless, does not shatter, and is not discolored by long exposure tolight.

This molding powder may be incorporated with inert fillers of all kinds,including pigments, and including also powdered glass wool which servesto give increased strength. The use of mixtures of powdered wools madefrom glass of various colors permits the formation of imitation opalsand the like.

The following illustrations are set forth by way of example only:

Example 1.300 gms. of granulated white sugar were dissolved in analuminum vessel in It is infusible at temperatures 250 cc. of 36%formalin solution at a sufficiently low temperature to preventcaramelization of the sugar. Heat was applied to the vessel and thetemperature gradually raised. vAs the temperature increased there was aslow evolution-of formaldehyde gas until the temperature reached a pointwhen there was a vigorous and very large increase of ebullition whichcontinued for a few moments and then, despite further increase of thetemperature, all evolution of gas ceased.

After the reaction between the sugar and the formalin had beencompleted, the temperature was raised still further and higher than thecaramelization point of the sugar without discoloration or darkening ofthe fluid in the vessel.

The purpose of this increase of temperature was to promote the expulsionof water vapor and was accompanied by boiling of the liquid. Durlng thisboilLng 10 gms. of hexamethylenetetramine were added as a hardeningagent, the liquid being stirred sufficiently to get thehexamethylenetetramine into solution. After the hexamethylenetetraminewas fully dissolved, the temperature was further increased withincreased boiling. There was now added to the solution in smallinstallments gms. of urea. This was sprinkled gently on the surface ofthe reaction mass in the vessel in twelve equal installments of about 6gms. each, with constant agitation and taking care to see that eachinstallment was fully dissolved before the next was added. This tookabout half an hour and during this period the heat was maintainedconsiderably above the boiling point of water and stirring wascontinuous. When the last of the urea had been dissolved the reactionmass was at once poured into molds.

Example 2.The process described under Example 1 was carried out in allrespects as stated, except that the addition of thehexamethylenetetramine was omitted. After the addition of, the urea, itwas found that the reaction mass rapid- 1y thickened till it could notbe poured; but when it was quickly transferred into molds before it hadbecome unpourable and allowed to harden therein it hardened to asubstance difiering from the substance made in accordance with Example 1in that neither further heating nor prolonged contact with the aircaused it to harden fully, and, on being broken up into powder and, hotpressed into molds, it continued to retain its yielding quality thoughbeing clear, transparent and water-white.

The reaction mass produced in accordance with Example 1 was in oneinstance poured into a mold, in another instance poured on a polishedmetal plate for drying in contact with the air, and in another instanceextruded as a rod.

The reaction mass of Example I poured into a mold was found to harden toa transparent, wa-

ter-white substance which was at first somewhat L 'r'.or was found to besomewhat less stress resistant than the exposed surface,but on exposureof the fractured surface to the air this assumed the hard characteristicof the other exposed surfaces.

It was found that the mass fully and accurately reproduced everyconfiguration of the mold, including minute scratches or marks.

The reaction mass of Example I poured on a polished metal plate rapidlyhardened in-the form of a thin sheet which when removed from the platewas found to have a surface of a highly polished appearance. Because ofthe thinness of the sheet, and the opportunity given after removal fromthe plate for curing both surfaces thereof in contact with the air, thesheet became very tough in a few days. It was highly transparent, havingbrilliant water-white characteristics, and was found to transmit ultraviolet rays to an extent greatly superior to that of glass andapproximately that of quartz.

The reaction mass of Example 1 extruded as a rod was broken up into amolding powder which was permitted to dry. This powder was then pressedinto molds under a pressure of about 1000 pounds per square inch at atemperature of 150 C. to form a clear transparent glass-like homogeneoussubstance similar in general physical characteristics to the pouredarticle, except that the substantial surface hardness of the pouredarticle was found to exist throughout the whole body of the pressedarticle.

The reaction mass produced in accordance with Example 2 was in oneinstance poured into a mold, in another instance poured on a polishedmetal plate for drying in contact with the air, and in another instanceextruded as a rod.

The reaction mass of Example 2 poured into a mold was found to harden toa resilient, waterwhite substance which was yielding and resilient andremained in that condition after removal of the mold and after prolongedexposure to the air. Its surface however was firm, dry and nontacky.When broken the interior was found to be somewhat softer and slightlytacky but on exposure of the fractured surface to the air it quicklybecame dry and non-tacky and gradually hardened somewhat.

The reaction mass of Example 2 poured on a polished metal sheet rapidlyacquired a dry and non-tacky surface but despite long exposure to theair remained resilient like soft rubber. It was highly transparent andbrilliantly waterwhite.

The reaction mass of Example 2 extruded as a rod was broken up into apowder and exposed to the air. To this powder was added 7% and 10% byweight of dry powdered crystals of hexamethylenetetramine, and after thetwo powders had been thoroughly incorporated together by stirring andkneading, they then constituted a molding powder which was pressed intomolds under a pressure of about 1000 pounds and at a temperature of 250C. A substance was formed in the mold having approximately the samecharacteristics as the poured or molded substance made in accordancewith Example 1.

The molding powder made in accordance with either of the methodsdisclosed above has a variety of fields of usefulness either alone or asa.

binder to be incorporated with suitable inert fillers in the preparationof tough durable molded articles which may have a wide range ofproperties depending on the ingredients selected. Thus, opacity may beobtained by the use of inert fillers such as ground-up synthetic ornatural resins or gums, waxes, fats, reclaimed rubber, cellulose nitrateor acetate, or the like, or synthetic condensation products.Water-resisting qualities may be obtained by the incorporation ofsuitable'oils such as castor or linseed oil. Transparency may beobtained by the use of powdered glass wool. Special effects may beobtained by the use of colored powdered glass wool, or combinations ofpowdered -glass wool of differing colors. Dielectric strength may beobtained by the addition of any inert non-metallic substances, includingthose named above, which serve to give strength and rigidity to themass.

The molding powder above referred to, when mixed with the othersubstances mentioned, may be pressed into molds under a pressure of 1000to 2000 pounds per square inch at a temperature of 150-350 C. Thus aresin may be produced, which has high tensile strength, and is capableof being machined, turned and polished.

Molded objects formed under pressure and composed of finely powderedglass wool and 10% of my molding powder, after being subjected to apressure of 2000 pounds per square inch and at 200 0., were found to beexceedingly hard. The mixing of finely chopped wool of colored glass,in'va'rious proportions, enabled me to produce a satisfactory imitationopal of a high degree of hardness.

My invention also enables me to produce filled resins by direct pouringand casting. Thus, to the heated reaction mass before it has so farhardened as to be unpourable, may be added inert fillers of many kinds,and in particular those inert fillers mentioned above in connection withfilled resins made from my molding powder. These may be introduced atany convenient stage of the heating process before the reaction mass hasthickened to such an extent as to make incorporation of thefillerimpossible. As an example of the foregoing, finely chopped sugarcane which has not been freed of sap may be used as the saccharide inthe initial stage of the reaction. In this case the cellulose particlesof the cane furnish an inert filling material and the reaction mass,after introduction of the urea, may be poured to provide a cellulosefilled resin by direct pouring and casting.

In accordance with the foregoing disclosure, I am able to make acomposition of matter having 15 among others the following properties:-

The poured or extruded substance of this invention may have varyingdegrees of hardness depending on whether a hardening agent such ashexamethylenetetramine is used, and also de- 2 pending on theproportions of urea added in the second stage of condensation orreaction. Thus my composition of matter may be made yielding orresilient, or it may be made as hard as very hard vulcanized rubber,within the invention. It is brilliantly clear and transparent and isperfectly water-white. Cast or pressed in sections having a thickness ofseveral inches it offers almost no obstacle to vision, and will transmitthe entire spectrum and especially the ultra violet 30 rays to an extentapproximating that of quartz. It is not thermo-plastic but will charsuperficially when strongly heated in the open air. It is free from anytrace of the odor of formaldehyde or any of the other ingredients. Itwill rotate the plane of transmitted light, so as do sugar crystals, butdiffers from sugar in most other properties. It is insoluble in most ofthe usual spirit solvents used singly but will dissolve in combinationof some of them. It is slightly softened, superficially, on longexposure to water. It will not shrink, crack or discolor on prolongedexposure to air or sunlight. It has high tensile strength and stressresistance in its hardened forms.

The molding powder of this invention may be employed as a binder in themaking of substances whose properties may vary within wide limitsdepending on the choice of the ingredients that are incorporated withthe molding powder. Among other properties which may be obtained by the5 use of my molding powder with suitable fillers are high dielectricstrength, extreme hardness, opacity or transparency, completewater-insolubility, and a choice of colors and color combinationsincluding especially effects obtained by suspending colored opaquebodies of large or small size within otherwise transparent bodies of mycomposition of matter.

The composition of matter herein disclosed, and the process of makingit, is not to be confused with the previously known therapeutic andmedicinal substances containing a sugar and formaldehyde. Thesesubstances are adapted to dissociate readily into antisepticformaldehyde and soluble sugar when brought into contact with livingtissue and differ in nearly all properties from the composition ofmatter disclosed hereinabove. They exist either as a liquid having noplastic properties or as a dry powder which lacks the properties of mymolding powder hereinabove described. Nor is my invention to be confusedwith the use of sugar as a filler or inert binder in connection withreactions or condensations between formaldehyde and urea wherein a smallamount of sugar is added to check the well-known tendency of aformaldehyde-urea resin to crack and crumble on standing.

I claim:

1. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a saccharideof the groupconsisting of monoand di-saccharides and an aldehyde, and urea.

2. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a sugar and an aldehyde, and

urea. f

3. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a saccharide of the groupconsisting of monoand di-saccharides and formaldehyde, and urea.

4. The process of making a plasticv substance which comprises reactingtogether the product of the reaction of a sugar and formaldehyde, and

urea.

5. The process of making a plastic substance which comprises heating to;ether a sugar and a substance capable of producing formaldehyde at thereaction temperature, and after the'reaction Is complete adding theretourea.

6. The process of making a plastic substance which comprises heatingtogether in liquid phase a sugar and a substance capable of producingformaldehyde at the reaction temperature, and after the reaction iscomplete adding to the liquid in a succession of small incrementssufficient urea to cause the liquid to become thickly viscous.

'7. The process of making a plastic substance which comprises heatingtogether in liquid phase a sugar and a substance capable of producingformaldehyde at the reaction temperature, and after the rea tion iscomplete adding to the liquid in a succession of small increments withagitation sufficient urea to cause the liquid to become thickly viscous.

8. The process of making a plastic substance which comprises heatingtogether in liquid phase a sugar and a substance capable of producing.

formaldehyde at 'the reaction temperature, and after the reaction iscomplete adding to the liquid in a succession of small incrementssufficient urea to cause the liquid to become thickly viscous andheating the viscous mass sufiiciently to cause it to harden to a plasticsolid.

9. The process of making a plastic substance which comprises heatingtogether in liquid phase a sugar and a substance capable of producingformaldehyde at the reaction temperature, and after the reaction iscomplete adding to the liquid in a succession of small increments withagitation sufficient urea to cause the liquid to become thickly viscousand heating the viscous mass surficiently to cause it to harden to aplastic solid.

10. A plastic substance formed by the reaction of urea with the productof the reaction of a sugar and a substance capable of producingformaldehyde at the reaction temperature.

11. A plastic resin consisting of the reaction product of urea with asugar-formaldehyde condensate.

12. A molding powder for use in forming plastic substances comprisingthe pulverized product of the reaction of urea with the product of thereaction of a sugar and a substance capable of producing formaldehyde atthe reaction temperature. i

13. A molding powder comprising the pulverized product by the'reactionof urea with a sugar- 'of monoand di-saccharides with a substancecapable of producing an aldehyde at the reaction temperature, and havinga hardening agent incorporated therein.

ARTHUR S. FORD.

CERTIFICATE OF CORRECTION.

Patent No. 1,949, 831.

March 6, 1934.

ARTHUR S. FORD.

It is hereby certified that error appears in the printed specificationof'the above numbered patent requiring correction asfol-lows: Page 2,line 73, for "300" read 300 C.; page 4, line 136-, strike out the word"so"; page 5, line 120, claim 13, for "by" read of; and that the saidLetters Patent should be read with these corrections therein that thesame may conform to the record of the case in the Patent Office.

(Seal) Bryan -M. Battey Acting Commissioner of Patents.

